A class of diaryl ethers and compositions thereof which are useful in the control of weeds is of the general formula 
wherein
X, Y are hydrogen, halogen, cyano, nitro, or (C1-6)haloalkyl;
Z is oxygen or sulfur,
Q is selected from 
Ar is a substituted or unsubstituted aryl or heteroaryl ring; When Q is Q3 or Q6, substituted phenyl is excluded.
Various substituted phenyl ethers (I1) are known in the literature. 
Q may be pyrazole, imidazole, imidazolidine-2,4-dione, triazolinone, tetrazolinone, aminouracil, etc. R may be hydrogen, alkyl, cycloalkyl, alkenyl or alkynyl. U.S. Pat. No. 5,496,956 discloses arylpyrazoles with the R group selected from propargyl, allyl, or substituted alkyl. JP 6,256,312 discloses phenylimidazoles with the R group selected from hydrogen, (C1-10akyl, (C1-5)haloalkyl, (C3-5)alkenyl, (C3-5)alkynyl, or (C3-6) cloalkyl. U.S. Pat. No. 5,125,958 discloses triazolinones with the R group selected from substituted phenyl group. JP 57,197,268 discloses hydantoins with the R group selected lower alkyl. U.S. Pat. No. 4,902,337 discloses hydantoins with the R group selected from hydrogen, alkyl, cycloalkyl, alkenyl or alkynyl. JP 525173 discloses pyrimidinediones with the R group selected from hydrogen, (C1-10)alkyl, (C1-5)haloalkyl, (C3-5)alkenyl, (C3-5)alkynyl, or (C3-6)cycloalkyl, U.S. Pat. No. 4,985,065 discloses phenyltetrazolinones with the R group selected from substituted phenyl group. No heteroaryl derivatives were claimed as R. WO 9,602,523 discloses substituted aryliminothiadiazoles with the R group selected from hydrogen, alkyl, cycloalkyl, alkenyl or alkynyl. U.S. Pat. No. 4,452,981 discloses phenylurazoles with the R group selected from (C1-3)alkyl, allyl, or propargyl. EP-A-517181(which corresponds to U.S. Pat. No. 5,280,010) discloses ammouracil compounds wherein Q is amino uracil and R is a lower alkyl group. WO96/07323 and WO96/08151 disclose some known uracil compounds. In WO96/08151 the generic representation is significantly broader than the disclosures set forth in it, and in the prior art patents. The specific aminouracil compounds of the formula (I) mentioned below are not known and are novel.
The present invention reveals that some diaryl ethers represented by the general formula (I) or their salts have a potent herbicidal activity with good crop safety.
The need continues for novel and improved herbicidal compounds and compositions. This invention relates to novel diaryl ethers, compositions comprising diaryl ethers, and the use of diaryl ethers and compositions thereof as broad spectrum herbicides which are effective against both monocot and dicot weed species in preemergence and postemergence application and are sometimes safe to crops. The compounds and compositions of the present invention can also be sometimes used as desiccants. This invention also includes methods of preparing these compounds and intermediates thereof as well as methods of using the compound as herbicides.
This invention relates to diaryl ether compounds having the general formula I and their salts 
wherein
X, Y are independently hydrogen, halogen, cyano, nitro, or (C1-6)haloalkyl and
Z is oxygen or sulfur and
Q is selected from 
R1 is halogen;
R2, R3, R4 and R5 are independently hydrogen, (C1-6)alkyl, or (C1-6)haloalkyl;
When R3 and R5 are taken together with the atoms to which they are attached, they represent a four to seven membered substituted or unsubstituted ring optionally interrupted by O, S(O)n or Nxe2x80x94R4, and optionally substituted with one to three (C1-6)alkyl group or one or more halogen atoms;
R6 is hydrogen, (C1-6)alkyl, (C2-6)alkenyl, (C2-6)alkynyl, (C1-6)haloalkyl, (C2-6)haloalkenyl, (C2-6)haloalkynyl, (C1-6)cyanoalkyl, (C1-6)alkoxy-(C1-6)alkyl, or (C1-6)alkylthio-(C1-6)alkyl;
A1 and A2 are independently oxygen or sulfur;
B is CH or N;
R7 and R8 are each independently hydrogen, (C1-6)alkyl optionally substituted with one or more halogen atoms, or (C3-C6)cycloalkyl optionally substituted with one or more halogen atoms, and when R7 and R8 are taken together with the atoms to which they are attached, they represent a four to seven membered substituted or unsubstituted ring optionally interrupted by O, S(O)n or Nxe2x80x94R4, and optionally substituted with one to three (C1-6)alkyl groups or one or more halogen atoms;
n is an integer of 0, 1, or 2.
R9 and R10 are hydrogen, (C1-6)alkyl, acyl, or (C1-6)alkylsulfonyl or R9 and R10 may form a ring consisting of polymethylene, (CH2)m groups, where m is an integer of 2, 3, 4 or 5, together with the nitrogen atom of NR9R10, which may or may not have a (C1-6)alkyl substituent.
Some compounds of formula (1) and their intermediates may occasionally exist as geometrical or optical isomers and the present invention includes all of these isomeric forms
Some compounds of the formula (I) and their intermediates may form a salt with an acidic substance or a basic substance. The salt with an acidic substance may be an inorganic acid salt such as a hydrochloride, a hydrobromide, a phosphate, a sulfate or a nitrate. The salt with a basic substance may be a salt of an inorganic or organic base such as a sodium salt, a potassium salt, a calcium salt, a quaternary ammonium salt such as ammonium salt or a dimethylamine salt.
Ar is a substituted or unsubstituted aryl or heteroaryl ring; When Q is Q3 or Q6, substituted phenyl is excluded.
This invention also relates to compositions containing those compounds and methods for using those compounds and compositions. The compounds and compositions of the present invention are especially useful for the selective control of undesirable plant species occasionally in the presence of crops. The compounds and compositions of the present invention can also be used as desiccants.
The present invention provides a method for controlling undesirable plant species by preemergence or postemergence application.
The diaryl ether compounds of this invention have the general formula I 
wherein X, Y, Z, Ar, and Q are as described above.
The aryl in the definition of Ar may be phenyl or naphthyl, and the heteroaryl in the definition of Ar may be a five or six membered ring having at least one heterogeneous atom of nitrogen, oxygen or sulfur, and for example may be pyridyl, pyrimidyl, pyridazinyl, triazolyl, thiazolyl or isothiazolyl. The substituents for the substituted aryl or heteroaryl ring may, for example, be halogen, (C1-6)alkyl, halo(C1-6)alkyl, (C1-6)alkoxy, halo(C1-6)alkoxy, (C1-6)alkylthio, (C1-6)alkylsulfonyl, (C1-6)alkylsulfinyl, (C1-6)dialkylaminocarbonyl, cyano, nitro, amino, hydroxy, (C1-6)alkylsulfonylamino, (C1-6)alkoxycarbonyl(C1-6)alkoxy, (C1-6)alkylcarbonylamino, bisbenzoylamino, aminoacetyl, aminotifluoroacetyl, or amino(C1-6)allylsulfonate. The number of substituents is one or more, for example up to five. When the number is two or more, the substituents may be same or different.
The alkyl group and alkyl part in the definition related to X, Y, R2 to R10 and the substituents for the substituted aryl and heteroaryl ring as Ar have the straighted or branched chains with C1-6 preferably C1-4 such as methyl, ethyl, propyl, butyl, pentyl, or hexyl. The alkenyl or alkynyl group and their parts in the definition for R6 have also the straighted or branched chains with C2-6, preferably C2-4 such as vinyl, propenyl, butenyl, pentenyl, hexenyl, ethynyl, propynyl, butynyl, pentynyl, or hexynyl.
The halogen atom and halogeno part in the definition related to X, Y, R1 to R8 are fluorine, chlorine, bromine, or iodine. The haloalkyl, haloalkenyl or haloalkynyl group constitutes the alkyl, alkenyl or alkynyl group and one or more halogen atoms as mentioned above. When the number of halogen atom is two or more, halogen atoms may be same or different.
Preferred formula I compounds of this invention are those wherein
X, Y are independently hydrogen, or halogen;
Z is oxygen or sulfur,
Q is selected from Q1, Q2, Q4, Q6, Q7, Q8, or Q9.
Ar is pyridyl, pyrimidyl, triazolyl, thiazolyl, isothiazolyl, or phenyl or pyridyl, pyrimidyl, triazolyl, thiazolyl, isothiazolyl, or phenyl substituted with up to five substituents independently selected from bromo, chloro, fluoro, iodo, (C1-C4)alkyl, halo(C1-4)alkyl, (C1-4)alkoxy, (C1-4)alkylthio, halo(C1-4)alkoxy, (C1-4)alkylsulfonyl, (C1-C3)alkylsulfinyl, di(C1-4)alkylaminocarbonyl, cyano, nitro, amino, hydroxy, (C1-4)alkylsulfonylamino, (C1-4)alkoxycarbonyl(C1-4)alkoxy, or (C1-4)alkoxycarbonylamino; When Q is Q6, substituted phenyl is excluded.
The most preferred formula I compounds of this invention are those wherein
X is fluorine;
Y is chlorine;
Z is oxygen or sulfur;
Q is selected from Q1, Q2, Q4, Q6, Q7, Q8, or Q9.
Ar is 2-pyridyl, 3-pyridyl , 4-pyridyl , 3-bromo-2-pyridyl, 5-bromo-2-pyridyl, 6-bromo-2-pyridyl, 3-chloro-2-pyridyl, 5-chloro-2-pyridyl, 6-chloro-2-pyridyl, 3-fluoro-2-pyridyl, 5-fluoro-2-pyridyl, 6-fluoro-2-pyridyl, 3-cyano-2-pyridyl, 5-cyano-2-pyridyl, 6-cyano-2-pyridyl, 3-nitro-2-pyridyl, 5-nitro-2-pyridyl, 6-nitro-2-pyridyl, 3-trifluoromethyl-2-pyridyl, 4-trifluoromethyl-2-pyridyl, 5-trifluoromethyl-2-pyridyl, 6-trifluoromethyl-2-pyridyl, 5-amino-2-pyridyl, 3-dimethylaminocarbonyl-2-pyridyl, 3-methylsulfonyl-2-pyridyl, 3-isopropylsulfonyl-2-pyridyl, 6-chloro-3-trifluoromethyl-2-pyridyl, 3,5,6-trifluoropyridyl, 2-pyrimidyl, 4-pyrimidyl, 5-bromo-2-pyrimidyl, 4-chloro-2-pyrimidyl, 4-trifluoromethyl-2-pyrimidyl, 4,6-dimethoxy-2-pyrimidyl, 2,6-dimethoxy-4-pyrimidyl, 4,6-dimethoxy-2-triazinyl, phenyl, 2-iodophenyl, 2-trifluoromethoxyphenyl, 2-nitrophenyl, 4-nitrophenyl, 4-aminophenyl, 4-hydroxyphenyl, 4-methylsulfonylaminophenyl, 4-(1-ethoxycarbonylethoxy)phenyl, 2-cyanophenyl, 2cyano-3-fluorophenyl, 2-cyano-4-fluorophenyl, 2-amino-4-(1-ethoxycarbonylethoxy)-phenyl, 2-cyano-4-nitrophenyl, 4-amino-2-cyanophenyl, 4-nitro-2-trifluoromethylphenyl, 4-amino-2-trifluoromethylphenyl, 4-acetylamino-2-trifluoromethylphenyl, 4-(1-ethoxycarbonylethoxy)-2-nitrophenyl, 5-chloro-4-(1-ethoxycarbonylethoxy)-2-nitrophenyl, 3-methyl4-nitro-5-isothiazolyl,or 5-nitro-2-thiazolyl; When Q is Q6 substituted phenyl is excluded.
The intermediates II and III can be prepared by the methods mentioned in Process (1). 
Process (1) is carried out in two stages. The first step is the reaction of an aminophenol with an aryl halide or an heteroaryl halide with or without solvents. The solvents may include acetonitrile, tetrahydrofuran, dimethyl imidazolidine, dimethylsulfoxide, hexamethylphosphoric triamide, N,N-dimethylformamide, acetone, butan-2-one, benzene, toluene or xylene, in the presence of a base such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, potassium t-butoxide, potassium fluoride, or sodium hydride. Catalysts may or may not be used . Such catalysts include copper(1)chloride, copper(1)oxide, copper, copper(1)alkoxide, alkyl cuprate, palladium(0), tetrabutylammonium halides, or 8-quinolinol. The reaction temperature is usually from 0xc2x0 C. to 250xc2x0 C., preferably from 20xc2x0 C. to 120xc2x0 C. The reaction time is from 1 to 12 hours, preferably from 2 to 6 hours. The diaryl ethers (II) may also be prepared by treatment of an aminophenol with aryl-lead tricarboxylates, triphenylbismuth-diacetate, triphenylbismuth-trifluoroacetate or diphenyliodonium halides in the presence of solvents such as benzene, toluene, dichloromethane, dichloroethane, chloroform or water, with or without catalysts such as copper, or a transition metal. The temperature is usually from 0xc2x0 C. to the reflux temperature of the mixture, and the reaction time from 10 minutes to 72 hours. The temperature is preferably from 20xc2x0 C. to the reflux temperature of the mixture, and the time preferably 2 to 6 hours.
The second step requires treatment of the amine (II) with phosgene or triphosgene in a solvent such as hexane, heptane, benzene, toluene, xylene, or ethyl acetates The reaction temperature is usually from 0xc2x0 C. to the reflux temperature of the mixture, preferably at the reflux temperature of the mixture. The reaction time is usually from 30 minutes to 6 hours, preferably from 2 to 3 hours. 
In Process (2) the ether linkage is formed using the conditions described in the first stage of Process (1). 
In Process (3) the ether linkage is formed using the conditions described in the first stage of Process (1). 
Process (4) proceeds in three stages. The first step is the formation of a diazonium salt of aniline (II) usually in an acidic medium such as conc. hydrochloric acid when treated with aqueous sodium nitrite solution. It is reduced in the presence of a reducing agent to give the corresponding hydrazine derivative. Such a reducing agent could be an inorganic compound such as hydrated tin(II)chloride. This is treated with a ketoacid such as pyruvic acid in aqueous solution. The reaction temperature is between xe2x88x9215xc2x0 C. to 30xc2x0 C. and the time from 30 minutes to 4 hours. The preferred temperature initially is between 0xc2x0 C. and 5xc2x0 C. and later at 20xc2x0 C. to 30xc2x0 C. and the preferred time is from 30 to 60 minutes.
In the second step the prepared hydrazone (VIII) is treated with diphenylphos-phoryl azide in an inert solvent such as benzene, toluene, xylene, hexane, in the presence of a base such as triethylamine or pyridine. The reaction temperature is between 20xc2x0 C. and the reflux temperature of the mixture and the time from 30 minutes to 6 hours. Preferably the temperature is the reflux temperature of the mixture and the time is from 1 to 2 hours.
The final stage is the alkylation of (IX) in an inert solvent such as diethyl ether, dioxane or tetrahydrofuran with an alkylating agent such as an alkyl halide, haloalkyl halide, or alkyl sulfate, in the presence of a base such as sodium or potassium hydroxide, sodium or potassium carbonate, pyridine or triethylamine with or without a catalytic amount of a tetraalkylammonium salt. The reaction temperature is between 40xc2x0 C. to 50xc2x0 C. and the time from 30 minutes to 4 days. The preferred reaction temperature is between 20xc2x0 C. to 30xc2x0 C., the preferred reaction time is 2 days. 
Process (5) proceeds in three stages. The first step is the treatment of the isocyanate (IIIa) with ammonia in an inert solvent such as hexane, benzene, toluene, xylene, diethyl ether, tetrahydrofuran or dioxane. The reaction temperature is between xe2x88x9210xc2x0 C. to 100xc2x0 C. and the time from 15 minutes to 6 hours. The reaction temperature is preferably between 0xc2x0 C. and 10xc2x0 C., and the time from 30 to 60 minutes.
The second step is the treatment of the urea (XI) with an acid catalyst such as p-toluenesulfonic acid or amberlyst resin, and a ketoester, in an inert solvent such as benzene, toluene, xylene, hexane, at a temperature between 20xc2x0 C. and the reflux temperature of the mixture, from 10 to 24 hours, to give the imidazolidinone (XII). The temperature is preferably the reflux temperature of the mixture and the time 12 to 16 hours.
The final stage is the alkylation of (XII) in an inert solvent such as diethyl ether, dioxane, tetrahydrofuran, benzene, toluene, xylene or hexane, with an alkylating agent such as an alkyl halide or haloalkyl halide, in the presence of a base such as sodium or potassium hydroxide, sodium or potassium carbonate, pyridine or triethylamine. The reaction temperature is between 20xc2x0 C. to the reflux temperature of the mixture, and the time from 30 minutes to 20 hours. Preferably the temperature is between 50xc2x0 C. and 100xc2x0 C. and the time from 12 to 16 hours. 
Process (6) proceeds in three stages. The first step is the treatment of the isocyanate (IIIb) with 2,2-dimethyl-5-(2-tetrahydropyrrolylidene)-1,3-dioxane4,6-dione in the presence of a base such as sodium methoxide, sodium ethoxide, potassium t-butoxide, or sodium hydride in a solvent such as toluene, N,N-dimethylformamide or dimethylsulfoxide. The reaction temperature is between xe2x88x9240xc2x0 C. to the reflux temperature of the mixture and the time from 30 minutes to 14 hours. Preferably the initial temperature of the addition is between xe2x88x9230xc2x0 C. to xe2x88x9220xc2x0 C., and further reaction requires temperatures of between 100xc2x0 C. and 120xc2x0 C. The preferred time is from 4 to 5 hours.
The second step is the hydrolysis of the ether linkage under acidic conditions in an inert solvent such as chloroform or methylene chloride, using conc. sulfuric acid. The reaction temperature is between xe2x88x9220xc2x0 C. to 50xc2x0 C. and the time from 30 minutes to 6 hours. Preferably the addition is done at between 0xc2x0 C. to 5xc2x0 C., and further reaction requires temperatures of between 20xc2x0 C. and 30xc2x0 C. The preferred time is from 1 to 2 hours.
In the final step the ether linkage is formed using the conditions described in the first stage of Process (1). 
Process (7) proceeds in two stages. The first step is the formation of the tetrazole ring (XVIII) by treatment of the isocyanate (III) with trimethylsilyl azide with or without solvent. The reaction temperature is between 100xc2x0 C. to the reflux temperature of the mixture and the time from 1 to 48 hours. Preferably the temperature is the reflux temperature of the mixture and the time 24 hours.
The final stage is the alkylation of (XVIII) in an inert solvent such as acetone, diethyl ether, dioxane, tetrahydrofuran, benzene, toluene, xylene, hexane, N,N-dimethyl-formamide or dimethylsulfoxide, with an alkylating agent such as an alkyl halide or an haloalkyl halide in the presence of a base such as sodium or potassium hydroxide, sodium or potassium carbonate, pyridine or triethylamine. The reaction temperature is between 50xc2x0 C. to 150xc2x0 C. and the time from 30 minutes to 2 days. The preferred temperature range is between 70xc2x0 C. and 90xc2x0 C. and the time from 20 to 30 hours. 
Process (8) proceeds in five stages. The first step requires treatment of the amine (II) with thiophosgene in a solvent such as hexane, heptane, benzene, toluene, xylene, or ethyl acetate. The reaction temperature is usually from 0xc2x0 C. to the reflux temperature of the mixture, preferably the addition is done at 0xc2x0 C. to 5xc2x0 C., and further reaction requires temperatures heating to the reflux temperature of the mixture. The reaction time is usually from 30 minutes to 6 hours, preferably from 2 to 3 hours.
In the second step the isothiocyanate (XX was treated with formic hydrazide in an inert solvent such as toluene, tetrahydrofuran, dioxane or diethyl ether. The reaction temperature is usually from 0xc2x0 C. to the reflux temperature of the mixture, preferably at ambient temperature. The reaction time is usually from 30 minutes to 10 hours, preferably from 3 to 4 hours.
The formyl hydrazines (XXI) were treated with phosgene or triphosgene in a solvent such as hexane, heptane, benzene, toluene, xylene, acetone, or ethyl acetate. The reaction temperature is usually from xe2x88x9220xc2x0 C. to 50xc2x0 C., preferably between 0xc2x0 C. and 25xc2x0 C. The reaction time is usually from 30 minutes to 6 hours, preferably from 1 to 2 hours.
The hydrolysis of the 3-formylthiadiazolidinones (XXII) is done under acidic conditions in such solvents as acetone, butan-2-one, methanol, ethanol, tetrahydrofuran, or N,N-dimethylformamide. The acids may be sulfuric, hydrochloric or acetic acids and may be diluted. The reaction temperature is usually from xe2x88x9220xc2x0 C. to 50xc2x0 C., preferably between 0xc2x0 C. and 25xc2x0 C. The reaction time is usually from 15 minutes to 6 hours, preferably from 30 minutes to 2 hours.
The final stage is the alkylation of (XXIII) in an inert solvent such as acetone, diethyl ether, dioxane, tetrahydrofuran, benzene, toluene, xylene, hexane, N,N-dimethyl-formamide or dimethylsulfoxide, with an alkylating agent such as an alkyl halide or a haloalkyl halide, in the presence of a base such as sodium or potassium hydroxide, sodium or potassium carbonate, pyridine or triethylamine. The reaction temperature is between 30xc2x0 C. to the reflux temperature of the mixture and the time from 30 minutes to 6 hours. The preferred temperature range is between 50xc2x0 C. and 90xc2x0 C. and the time from 1 to 3 hours. 
In Process (9) amines (II) are transformed into the 2,4-imidazolidinediones (XXVII) in three stages. In the first step treatment with a haloacetyl halide, such as chloroacetyl chloride and an organic base such as triethylamine or pyridine, in an inert solvent such as benzene, toluene, xylene, tetrahydrofuran, or N,N-dimethylformamide gave the chloroamides (XXV). The preferred acylating agent is chloroacetyl chloride and the preferred base triethylamine. The preferred solvent is toluene. The reaction may be carried out at temperatures between xe2x88x9220xc2x0 C. and 150xc2x0 C., preferably between 25xc2x0 C. and 50xc2x0 C. The reaction time may be from 30 minutes to ten hours, preferably between 2 and4 hours.
In the second step reaction of these chloroamides (XXV) with suitable amines in a solvent such as C1-5 alcohols, tetrahydrofuran, or dioxane gave amino-amides (XXVI). The preferred solvent is ethanol, and the reaction may be carried out at temperatures between xe2x88x9220xc2x0 C. and 150xc2x0 C., preferably between 25xc2x0 C. and 70xc2x0 C. The reaction time may be from 30 minutes to ten hours, preferably between 2 and 3 hours.
In the third step the amino-amides (XXVI are treated with 1,11-carbonyldi-imidazole in an inert solvent such as benzene, toluene, xylene, tetrahydrofuran, or N,N-dimethylformamide and yielded the 2,4-imidazlidinediones(XXVI). The preferred solvent is toluene, and the reaction may be carried out at temperatures between xe2x88x9220xc2x0 C. and 150xc2x0 C., preferably between 100xc2x0 C. and 120xc2x0 C. The reaction time may be from 30 minutes to ten hours, preferably between 2 and 3 hours. 
Process (10) proceeds in three stages. The first is the reaction of isothiocyanates (XXa) with a saturated cyclic heterocycle (XXVIII) such as 1-ethyloxycarbonylhexahydropyridazine, where B=N and f=2, and may or may not be done in two parts, (1) and (2). In part (1) they are stirred together in an inert solvent such as benzene, toluene, xylene, dioxane, hexane, ethyl acetate, tetrahydrofuran, diethyl ether, or acetone. The reaction temperature is usually from xe2x88x9270xc2x0 C. to the reflux temperature of the mixture, depending on the nature of B, f, and R4. The reaction time is usually from 30 minutes to 20 hours, depending on the nature of B, f, and R4. In part (2) after removal of the solvent toluene, xylene, or dioxane may be added, and also a weakly basic compound such as sodium acetate. The reaction proceeds at a temperature of between 50xc2x0 C. to the reflux temperature of the mixture and the time from 6 hours to 3 days. The preferred temperature is the reflux temperature of the mixture and the time from 20 to 30 hours.
The second step is the hydrolysis of the ether linkage under acidic conditions in an inert solvent such as chloroform or methylene chloride, using conc. sulfuric acid. The reaction temperature is between xe2x88x9220xc2x0 C. to 50xc2x0 C. and the time from 30 minutes to 6 hours. Preferably at 0xc2x0 C. and a time of 1 to 2 hours.
The final step is the formation of the ether linkage to give (XXXI). This is done using the conditions described in the first stage of Process (1). 
Process (11) is a one step process where a compound (XXb), which may be an isocyanate or an isothiocyanate, reacts with a saturated cyclic heterocycle (XXVIII), with or without solvents, to give the product (XXXI). The reaction is enhanced by the presence of solvents such as hexane, pentane, benzene, toluene, xylene, diethyl ether, tetrahydro-furan, dioxane, acetone, butan-2-one, ethyl acetate, N,N-dimethylformamide or dimethyl-sulfoxide, and is conducted between xe2x88x9270xc2x0 C. to the reflux temperature of the mixture and from 15 minutes to 20 hours. The temperature is preferably between 0xc2x0 C. and 30xc2x0 C., and the time from 15 minutes to 12 hours. 
In Process (12) the thiadiazabicyclononanones (XXIV) are treated with a catalytic amount of a base such as sodium methoxide, sodium ethoxide, or potassium t-butoxide in a C1-5 alcohol such as methanol, ethanol or t-butanol, at a temperature between 0xc2x0 C. and the reflux temperature of the mixture from 15 minutes to 3 hours. Preferably at the reflux temperature of the mixture and from 30 to 60 minutes. 
Process (13) is carried out using 0.5 to 10 equivalents (preferably 0.8 to 3) of the hydrazines relative to the oxazines (XXXII). Examples of hydrazines include hydrazine, alkyl hydrazines such as methyl, ethyl, or t-butylhydrazine, and cyclic hydrazines such as 1-aminopyrrolidine. The reaction proceeds without any solvents but is normally accelerated by employing solvent.
Further reaction requires solvents such as aliphatic hydrocarbons e,g, hexane, heptane, ligroin and petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, halogenated hydrocarbons such as chloroform and methylene chloride, ethers such as diethyl ether, dioxane, and tetrahydrofuran, ketones such as acetone and methyl ethyl ketones, nitrites such as acetonitrile and isobutyronitrile, tertiary amines such as pyridine and N,N-dimethylaniline, acid amides such as N,N-dimethyl-acetamide, N,N-dimethylformamide, and N-methylpyrrolidone, sulfur containing compounds such as dimethylsulfoxide and sulfolane, alcohols such as methanol, ethanol, propanol, and butanol, water and the mixtures thereof.
The reaction temperature is usually from xe2x88x9230xc2x0 C. to 150xc2x0 C., preferably from xe2x88x9210xc2x0 C. to the reflux temperature of the reaction mixture. The reaction time requires normally from 10 minutes to 96 hours, preferably from 30 minutes to 48 hours. 
In Process (14) the ether linkage is formed using the conditions described in the first stage of Process (1). 
Process (15) is carried out in a solvent such as dioxane, dimethylsulfoxide, hexamethylphosphoric triamide or N,N-dimethylformamide in the presence of a base such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, or sodium hydride. A number of aminating agents may be used such as 2,4-dinitro-phenoxyamine; O-arylsulfonylhydroxyamines such as 2,3,6-trimethyl- and triisopropyl-phenylhydroxyamine; O-picoylhydroxyamine; and O-mesitylhydroxyamine. The reaction temperature is usually from xe2x88x9230xc2x0 C. to 110xc2x0 C., and the reaction time is from 12 hours to 7 days. The reaction temperature is preferably from 20xc2x0 C. to 30xc2x0 C. The reaction time is preferably from 12 hours to 3 days. 
Using Process (16) the isocyanate (III) may be used to form the aminouracil (XXXIIa) in a one pot synthesis without isolating the uracil (XXXV). The uracil ring is formed by reacting the prepared isocyanate (III) with an alkyl 3-amino4,4,4-trifluoro-crotonate and a base such as sodium hydride, sodium methoxide or sodium ethoxide, in a solvent such as dimethylsulfoxide, N,N-dimethylformamide, benzene, toluene, xylene, tetrahydrofuran, dioxane, or diethyl ether, at temperatures usually from xe2x88x9250xc2x0 C. to 50xc2x0 C., with a reaction time from 10 minutes to 14 hours. Preferably between xe2x88x9230xc2x0 C. to 30xc2x0 C., with a reaction time of 15 minutes to 6 hours. Aminating agents, such as 2,4-dinitro-phenoxyamine; O-arylsulfonylhydroxyamines such as 2,3,6-trimethyl- and triisopropyl-phenylhydroxyamine; O-picoylhydroxyamine; and O-mesitylhydroxyamine are then introduced, as described for Process (15). The reaction temperature is usually from xe2x88x9230xc2x0 C. to 110xc2x0 C., and the reaction time is from 12 hours to 7 days. The reaction temperature is preferably from 20xc2x0 C. to 30xc2x0 C. The reaction time is preferably from 12 hours to 3 days. 
Using Process (17) a compound of formula (Q9) wherein A1 and/or A2 are/is a sulfur atom, can be prepared by reacting a compound of the above formula (XXXIII) with a sulfurizing agent such as Lawesson""s reagent or phosphorus pentasulfide. Further sulfurization may occur with prolonged heating and with excess reagent. The reaction uses solvents such as benzene, toluene and xylene. The reaction time is usually 2 to 12 hours, preferably 3 to 4 hours. The reaction temperature is usually 0xc2x0 C. to 150xc2x0 C., preferably between 60xc2x0 C. and the reflux temperature of the mixture. 
In Process (18) the ether linkage is formed using the conditions described in the first stage of Process (1). 
Process (19) requires the reaction of the sodium or potassium salt of an aromatic- or heterocyclic hydroxyl compound with the haloaromatic uracil (XXXVIII). The reaction proceeds without any solvent but is normally accelerated by employing solvent These include toluene, xylene, N,N-dimethylformamide, and dimethylsulfoxide, and a catalyst is used such as copper, copper bronze, or a transition metal. The temperature is usually from 0xc2x0 C. to 150xc2x0 C., and the reaction time from 10 minutes to 72 hours. The temperature is preferably from 150xc2x0 C. to the reflux temperature of the mixture, and the time preferably 2 to 6 hours. 
Process (20) shows how the uracil ring may be formed by reacting the prepared isocyanate (m) with an alkyl 3-amino-4,4,4-trifluorocrotonate and a base such as sodium hydride, sodium methoxide, sodium ethoxide, or potassium t-butoxide, in a solvent such as dimethylsulfoxide, N,N-dimethylformamide, benzene, toluene, xylene, tetrahydrofuran, dioxane, or diethyl ether, at temperatures usually from xe2x88x9250xc2x0 C. to 50xc2x0 C., with a reaction time from 10 minutes to 14 hours. Preferably from xe2x88x9230xc2x0 C. to 30xc2x0 C., with a reaction time of 15 minutes to 6 hours. 
Process (21) is carried out in two stages. The first step is the preparation of N-phenyl-acetamide (XXXIX) using conventional methodology.
The second step is the cyclization to give the oxazines (XXXII). This is carried out in solvents which are aliphatic hydrocarbons such as hexane, heptane, ligroin, and petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, and chloro-benzene, tertiary amines such as pyridine, and N,N-diethylaniline, acid amides such as N,N-dimethylacetamide, N,N-dimethylformamide, and N-methylpyrrolidone, sulfur containing compounds such as dimethylsulfoxide and sulfolane, and organic acids such as formic acid, acetic acid, lactic acid, and acetic anhydride. Preferably used are the above mentioned aliphatic hydrocarbons, aromatic hydrocarbons and organic acids. The reaction temperature is usually from 0xc2x0 C. to 200xc2x0 C., preferably from 20xc2x0 C. to the reflux temperature of the mixture. The reaction time is from 10 minutes to 72 hours, preferably from 30 minutes to 24 hours. 
Process (22) is carried out in two stages. The first step is the formation of the phenolic oxazine (XL) using the methodology described in Process (21). This is carried out in solvents which are aliphatic hydrocarbons such as hexane, heptane, ligroin, and petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, tertiary amines such as pyridine, and N,N-diethylaniline, acid amides such as N,N-dimethylacetamide, N,N-dimethylformamide, and N-methylpyrrolidone, sulfur containing compounds such as dimethylsulfoxide and sulfolane, and organic acids such as formic acid, acetic acid, lactic acid, and acetic anhydride. Preferably used arc the above mentioned aliphatic hydrocarbons, aromatic hydrocarbons and organic acids. The reaction temperature is usually from 0xc2x0 C. to 200xc2x0 C., preferably from 20xc2x0 C. to the reflux temperature of the mixture. The reaction time is from 10 minutes to 72 hours, preferably from 30 minutes to 24 hours.
The second step is carried out under the same conditions described for Process (13). 
Process (23) is carried out in two stages. The starting material for the first step, carbamates (XLI), are prepared by conventional methodology. These are treated with an alkyl 3-amino-4,4,4-trifluorocrotonate under the conditions described for Process (20). The second step is carried out under the same conditions described for Process (15). 
In Process (24) the isocyanate (III) is treated with the hydrazono compound (XLIII) under the conditions described for Process (20) to give the desired product (XXXIII).
Although some embodiments of the present invention are described as follows, the scope of the present invention is not limited to such an embodiment.
Preparation Examples for the compounds of the present invention will be described. The preparation of 3-chloro-2-fluoro-5-hydroxyphenyl)-6-trifluoronethyl-1,2,3,4-tetrahydropyrimidine-2,4-dione is described in U.S. Pat. No. 4,859,229. Lawesson""s reagent, [2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide], was obtained from Aldrich.